Certain amine-modified thermoplastic phenol-aldehyde resin salts and method of making same



States Patent Ofiice Patented J u'n 1 7-, 1 958 CERTAIN AMINE-MODEFIEDTHERMOPLASTIC PHENGL-ALDEHYDE RESIN SALTS AND METH- OF MAKING SAlviEMelvin De Groote, St. Louis, Mi, assignor to Petrolite Corporation,Wilmington, Del., a corporation of Delaware No Drawing. Originalapplication January 2, 1953, Se-

rial No. 329,486. Divided and this application April 9, 1956, Serial No.576,821

8 Claims. Cl. 260-43) The present invention is a continuation-in-part ofmy two co-pending applications, Serial No. 288,746, filed May 19, 1952,now abandoned, and Serial No. 296,087, filed June 27, 1952, now U. S.Patent 2,679,488, and a division of my co-pending application Serial No;329,486, filed January 2, 1953, now Patent No. 2,771,444.

My invention is concerned with new chemical products or compounds usefulas demulsifying agents in processes or procedures particularly adaptedfor preventing, breaking or resolving emulsions of the water-in-oil typeand particularly petroleum emulsions. My invention is also concernedwith the application of such chemical products or compounds in variousother arts and industries as well as with methods of manufacturing thenew che1nical products or compounds which are of outstanding value indemulsification.

My aforementioned co-pending application, Serial No. 288,746, filed May19, 1952, is concerned with the process of condensing certainphenol-aldehyde resins, therein described in detail, with certain cyclicamidines, also therein described in detail, and formaldehyde.

The present invention is concerned with the aforementioned amino resincondensates in the form of a gluconic acid salt, i. e., a form in whichall or part of the basic nitrogen atoms are neutralized with gluconicacid, i. e., converted into the salt of gluconic acid.

My aforementioned co-pending application, Serial No. 296,087, filed June27, 1952, is concerned with a process for breaking petroleum emulsionsof the water-in-oil type characterized by subjecting the emulsion to theaction of the amine resin condensates described in the aforementionedapplication Serial No. 288,746.

Needless to say, all that is required is to prepare the amine resincondensates in the manner described in the two aforementioned co-pendingapplications, and then neutralize with gluconic acid which, forpractical purposes is as simple as analogous inorganic reactions.

As far as the use of the herein described products goes for purpose ofresolution of petroleum emulsions of the water-in-oil type, Iparticularly prefer to use the gluconic acid salt of those members whichhave sufficient hydrophile character to meet at least the test as setforth in U. S. Patent No. 2,499,368 dated March 7, 1950, to De Groote etal. In said patent such test for emulsification using a water-insolublesolvent, generally xylene, is described as an index of surface activity.

The present invention involves the surface-activity of the gluconic acidsalts, i. e., either where only one basic amino nitrogen atom isneutralized or where all basic amino nitrogen atoms are neutralized.Such gluconic acid salts may not necessarily be xylene-soluble. If suchcompounds are not Xylene-soluble the obvious chemical equivalent orequivalent chemical test can be made by simply using some suitablesolvent, preferably a watersoluble solvent such as ethylene glycoldiethylether, or a low molal alcohol, or a mixture to dissolve theappropriate product being examined and then mix with the equal weight ofXylene, followed by addition of water.

2 Such test is obviously the same'for the reason that there will be twophases on vigorous shaking and surface activity makes its presencemanifest. It is understodd the reference in the hereto appended claimsas to the use of Xylene in the emulsification test includes such obviousvariant.

For convenience, what is said hereinafter will be divided into sevenparts: 7

Part 1 is concerned with the general structure of the amine-modifiedresins which are converted into the gluconic acid salt;

Part 2 is concerned with the phenol-aldehyde resin which is subjected tomodification by condensation reaction to yield the amine modified resin;

Part 3 is concerned with suitable basic amidines which may be employedin the preparation of the herein de scribed amine-modified resins;

Part 4 is concerned with the reactions involving the resin, the amidine,and formaldehyde to produce the specific products or compounds which areneutralized subsequently with gluconic acid;

Part 5 is concerned with the conversion of the basic condensate into thecorresponding salt of gluconic acid;

Part 6 is concerned with the resolution of petroleum emulsions of thewater-in-oil type by means of the previously described chemicalcompounds or reactions products in the form of gluconic acid salts; and

Part 7 is concerned with the uses for the products herein described,either as such or after modification, including any applications otherthan those involving resolution of petroleumcrnulsions of thewater-in-oil type. This part is limited also to the use of the gluconicacid salts. I

For reasons which are obvious, partibularly for con venience and ease ofcomparison, Parts 1, 2, 3 and 4 are in substantially verbatim form asthey appear in the two aforementioned co-pending applications, SerialNos. 288,746 and 296,087, and particularly as they appear in the latter.

PART 1 The compounds herein describedand particularly useful asdemulsifying agents are gluconic acid salts of heatstable andoxyalkylation susceptible resinous condensation products of certainphenolaldehyde resins, cyclic amidines and formaldehyde described inapplications Serial Nos. 288,746 and 296,087 to which reference is madefor a discussion of the general structure of such resins. p v

These resins may beeXemplified by an idealized formula which may, inpart, be an over-simplification in an effort to present certain resinstructure. Such formula would be the following:

in which R represents an aliphatic hydrocarbon s'ubstitu'ent generallyhaving four and not over 18 carbon atoms but most preferably not over 14carbon atoms, and n generally is a small Whole number varying from 1 to4. In the resin structure it is shown as being derived from formaldehydealthough obviously other aldehydes are equally satisfactory. The amineresidue in the above structure is derived from either a substitutedimidazoline or a substituted tetrahydropyrirnid'ine as previouslyspecified and may be indicated thus:

in which HN represents a reactive secondary amino group and twooccurrences of R represent the remainder of the molecule. Stated anotherway, what has been depicted in the above formula is anover-simplification as far as the ring compound is concerned which isobvious by reference to a more elaborate formula depicting the actualstructure of typical members of the group, such as:

N- H2 C H O N-C H:

C ;H4.NH. C:H4-NH. C 10H 2-methy1, l-hexadecylaminoetbylaminoethyllmidazoline Cums-O CsHt H 2 4.N

N-O H:

/C H: C a iN 2-heptadecyLl-methylaminoethyl tetrahydropyrimidine Theintroduction of two such ring compound radicals into a comparativelysmall resin molecule, for instance, one having 3 to 6 phenolic nuclei asspecified, alters the product in a number of ways. In the first place, abasic nitrogen atom, of course, adds a hydrophile effect; in the secondplace, depending on the size of the radical R,

' there may be a counterbalancing hydrophobe effect or one in which thehydrophobe effect more than counterbalances the hydrophile effect of thenitrogen atom. Finally, in such cases where R contains one or moreoxygen atoms, another effect is introduced, particularly anotherhydrophile effect. In such instances where there are hydroxyl groupspresents, needless to say there is a further hydrophile efiectintroduced.

The resins employed as raw materials in the instant procedure arecharacterized by the presence of an aliphatic radical in the ortho orpara position, i. e., the phenols themselves are difunctional phenols.

The resins herein employed contain only two terminal groups which arereactive to formaldehyde, i. e., they are difunctional from thestandpoint of methylol-forming reactions. As is well known, although onemay start with difunctional phenols, and depending on the procedureemployed, one may obtain cross-linking which indicates that one or moreof the phenolic nuclei have been converted from a difunctional radicalto a trifunctional radical, or in terms of the resin, the molecule as awhole has a methylol-forming reactivity greater than 2. Such shift cantake place after the resin has been formed or during resin formation.Briefly, an example is simply where an alkyl radical, such as methyl,ethyl, propyl, butyl, or the like, shifts from an ortho position to ameta position, or from a para position to a meta position. For instance,in the case of phenol-aldehyde varnish resins, one can prepare at leastsome in which the resins, instead of having only two points of reactioncan have three, and pos sibly more points of reaction, withformaldehyde, or any other reactant which tends to form a methylol orsubstituted methylol group.

The resins herein employed are soluble in a non-oxygenated hydrocarbonsolvent, such as benzene or xylene.

The resins herein employed as raw materials must be comparatively lowmolal products having on the average 3 to 6 nuclei per resin molecule.

The condensation products here obtained, whether in the form of the freebase or the salt, do not go over to the insoluble stage on heating. Thecondensation product obtained according to the present invention is heatstable and, in fact, one of its outstanding qualities is that it can besubjected to oxyalkylation, particularly oxyethylation oroxypropylation, under conventional conditions, i. e., presence of analkaline catalyst, for example, but in any event at a temperature aboveC. without becoming an insoluble mass.

Although these condensation products have been prepared primarily withthe thought in mind that they are precursors for subsequent reaction,yet as such and without further reaction, they have definitely valuableproperties and uses as hereinafter pointed out.

What has been said previously in regard to heat stability, particularlywhen employed as a reactant for preparation of derivatives, is stillimportant from the standpoint of manufacture of the condensationproducts themselves insofar that in the condensation process employed inpreparing the compounds described subsequently in detail, there is noobjection to the employing of a tempera ture above the boiling point ofwater. As a matter of fact, all the examples included subsequentlyemploy temperatures going up to to C.

What is said above deserves further amplification at this point for thereason that it may shorten what is said subsequently in regard to theproduction of the herein described condensation products. Sinceformaldehyde generally is employed economically in an aqueous phase (30%to 40% solution, for example) it is necessary to have manufacturingprocedure which will allow reactions to take place at the interface ofthe two immiscible liquids, to wit, the formaldehyde solution and theresin solution, on the assumption that generally the amine will dissolvein one phase or the other. Although reactions of the kind hereindescribed will begin at least at comparatively low temperatures, forinstance, 30 C., 40 C., or 50 0, yet the reaction does not go tocompletion except by the use of the higher temperatures. The use ofhigher temperatures means, of course, that the condensation productobtained at the end of the reaction must not be heatreactive. Of course,one can add an oxygenated solvent such as alcohol, dioxane, variousethers of glycols, or the like, and produce a homogeneous phase. If thislatter procedure is employed in preparing the herein describedcondensations it is purely a matter of convenience, but whether it is ornot, ultimately the temperature must still pass within the zoneindicated elsewhere, i. e., somewhere above the boiling point of Waterunless some obvious equivalent procedure is used.

Any reference, as in the hereto appended claims, to the procedureemployed in the process is not intended to limit the method or order inwhich the reactants are added, commingled or reacted. The procedure hasbeen referred to as a condensation process for obvious reasons. Aspointed out elsewhere it is my preference to dissolve the resin in asuitable solvent, add the amine, and then add the formaldehyde as a 37%solution. However, all three reactants can be added in any order. I aminclined to believe that in the presence of a basic catalyst, such asthe amine employed, that the formaldehyde produces methylol groupsattached to the phenolic nuclei which, in turn, react with the amine. Itwould be immaterial, of course, if the formaldehyde reacted with theamine so as to introduce a methylol group, attached to nitrogen which,in turn, would react with the resin molecule.

PART 2 OH Hr H1 0.. alien In the above formula n represents a smallwhole number varying from 1 to 6, 7 or 8, or more, up to probably 10 or12 units, particularly when the resin is subjected to heating under avacuum as described in the literature. A limited sub-genus is in theinstance of low molecular weight polymers where the total number ofphenol nuclei varies from 3 to 6, i. e., n varies from 1 to 4; Rrepresents an aliphatic hydrocarbon substituent, generally an alkylradical having from 4 to 14 carbon atoms, such as butyl, amyl, hexyl,decyl or dodecyl radical. Where the divalent bridge radical is shown asbeing derived from formaldehyde it may, of course, be derived from anyother reactive aldehyde having 8 carbon atoms or less.

The resins herein employed as raw materials must be soluble in anonoxygenated solvent, such as benzene or xylene. This presents noproblem insofar that all that is required is to make a solubility teston commercially available resins, or else prepare resins which arexyleneor benzene-soluble as described in aforementioned U. S. Patent No.2,499,365, or in U. S. Patent No. 2,499,368 dated March 7, 1950, to De'Groote and Kei'ser.

If one selected a resin of the kind just described previously andreacted approximately one mole of the resin with two moles offormaldehyde and two moles of a basic nonhydroxylated secondary amine asspecified, following the same idealized over-simplification previouslyreferred to, the resultant product might be illustrated thus:

ondary amine radical present and that the ring compound, or rather thetwo occurrences of R' jointly with n, be

free from a primary amine radical. However, if one attempts toincorporate into the formula r 6 a structure such as a substitutedimidazoline or substituted tetrahydropyrimidine such as the following:

NCH2 CHEW-G N-CHz CzHAOH then one becomes involved in added diflicultiesin presenting an overall picture. Thus, for sake of simplicity the ringcompound having the reactive secondary amino group will be depicted assubject to the limitation and explanation previously noted.

In conducting reactions of this kind one does not necessarily obtain ahundred percent yield for obvious reasons. Certain side reactions maytake place. For instance, 2 moles of amine may combine with one mole ofthe aldehyde, or only one mole-of the amine may combine with the resinmolecule, or even to a very slight extent, if at all, 2 resin units maycombine without any amine in the reaction product, as indicated in thefollowing formulas:

As has been pointed out previously, as far as the resin unit goes onecan use a mole of aldehyde other than formaldehyde, such asacetaldehyde, propionaldehyde or butyraldehyde. The resin unit may beexemplified thus:

in which R is the divalent radical obtained from the particular aldehydeemployed to form the resin. For reasons which are obvious thecondensation product obtained appears to be described best in terms ofthe method of manufacture.

As previously stated the preparation of resins, the kind herein employedas reactants, is well known. See previously mentioned U. S. Patent2,499,368. Resins can be made using an acid catalyst or basic catalystor a catalyst having neither acid nor basic properties in the ordinarysense or without any catalyst at all. -It is preferable that the resinsemployed be substantially neutral. In other words, if prepared by usinga strong acid as a catalyst, such strong acid should be neutralized.Similarly, if a stron base is used as a catalyst .it is preferable thatthe base be neutralized although I have found that sometimes thereaction described proceededmore rapidly in the presence of a smallamount of a free base. The amount may be as small as a 200th of apercent and as much as a few lOths of a percent. Sometimes moderateincrease in caustic soda and caustic potash may be used.

and their preparation.

However, the most desirable procedure in practically every case is tohave the resin neutral.

In preparing resins one does not get a single polymer,

i. e., one havingjust 3 units, or just 4 units, or just 5 units, or just6 units, etc. It is usually a mixture; for instance, one approximating 4phenolic nuclei will have 10 some trimer and pentamer present. Thus, themolecular weight may be such that it corresponds to a fractional valuefor n as, for example, 3.5, 4.5 or 5.2.

In the actual manufacture of the resins I found no reason for usingother than those which are lowest in price and most readily availablecommercially. For purposes of convenience suitable resins arecharacterized in the following table:

TABLE I M01. wt

Ex- Position 3 of resin ample R of R derived n molecul number from(based on n+2) 2a Tertiarybutyl Para; Formal- 3 6 882.5

Secondary butyl. Ortho 3.5 882. 5 Tertiary amyl Para. 3.6 959.5 Mixedsecondary Ortho... 3.5 805.5

andtertiaryamyl. 3O 1 3.5 805.5 3.5 1,036.5 3.5 1,100.5 3. 5 1, 267. 53.5 1,344.5 y 3.5 1, 498.5 Tertiary butyl 3.5 945.5 Tertiary amyl .do3.5 1, 022.5 Nonyl do..... 3.5 1, 330.5 Tertiary butyl do. 3.5 ,071.5

Tertiary amyl do.. 3.5 1,148.6 Nonyl 2... .do .do. 3.5 1, 456.5 Tertiarybutyl ...d0 Propional- 3.5 1,008.5 40

dehyde. Tertiary amyl do do 3.5 1,085.5 Nonyl do do.. 3.5 1,393.5Tertiary butyl .do Formal- 4. 2 995.6

dehyde. Tertiary amyl l 4.2 1,083.4 Non 4.2 1,430.6

PART 3 The expression cyclic amidines" is employed in its usual sense toindicate ring compounds in which there are present either 5 members or 6members, and having 2 nitrogen atoms separated by a single carbon atomsupplemented by either two additional carbon atoms or three additionalcarbon atoms completing the ring. All the carbon atoms may besubstituted. The nitrogen atom of the ring involving two monovalentlinkages may be substituted. Needless to say, these compounds includemembers in which the substituents also may have one or more nitrogenatoms, either in the form of amino-nitrogen atoms or in the form ofacylated nitrogen atoms. Reference is made to applications Serial Nos.288,746 and 296,087 for a detailed description of suitable .amidines 7-8 Examplesselected from the patents. include the following: NCH2C11H2a.O

N-OH1 CQH4.NH.C2H4.NH.C1QH33 V (s)2methyl,l-hexadecylaminoethylaminoethylimidazoline NCH7 H.O\

N-OH2 HmNI'LCnH (6) 1-dodecylamlnopropylimidazoline NCH:

r CQH4.NH.OQH4OCH.C17H35 (7) 1- stearoyloxyethyl aminoethylimidazolineN-OH;

O H ,NH .GzH4NH0C.C17H35 (8) l-stearamidoethylaminoethylimidazoline N CH:

GzH4.N.CgH4.NHO C-CHa iz zs 1- (N-dodecyl-acetamidoethylaminoethylimidazoiine NOHCH3 C11 a5C NCHOH3 (10)2-heptadecyL4,S-dimethylimidazoline NOH 11O\ N C H:

C0H12.NH.C12H25 V 1-dodecylarnlnohexylimidazoline N-O H2 N H: lgHmNH.02114. 0 0181135 l-etearoyloxyethy]aminohexylimidazoline N-CH:

CH BI -C CH; C2H N 2-heptadecyl,l-methylaminoethyl tetrahydropyrlmldlne4-methyl,2-dodecyl,l-methylaminoethylarninoethyl tetrahydropyrimidine Ashas been pointed out previously, the reactants herein employed may havetwo substituted imidazoline rings or two substitutedtetrahydropyrimidine rings. Such compounds are illustrated by thefollowing formula:

CHz-N H-CHz N As to compounds having a tertiary amine radical, it isobvious that one can employ derivatives of polyamines in which theterminal groups are unsymmetrically alkylated. Initial polyamines ofthis type are illustrated by the following formula:

in which R represents a small alkyl radical such as methyl, ethyl,propyl, etc., and n represents a small whole number greater than unitysuch as 2, 3 or 4.

Ring compounds, such as substituted imidazolines, may be reacted with asubstantial amount of alkylene oxide as noted and then a secondary aminogroup introduced amino radical can be subjected to acylationnotwithstanding the fact that the surveying amino group has nosignificant basicity. As a rule acylation takes place at the terminalprimary amino group rather than at the secondary amino group, thus onecan employ a compound such as C2H4.NH.G2H4.NH22-heptadecyl,l-diethyleuediaminoimidazoline and subject it to acylationso as to obtain, for example, acetylated2-heptadecy1,1-diethylenediaminoimidazoline of the following structure:

Similarly, a compound having no basic secondary amino radical but abasic primary amino radical can be reacted with a mole of an alkyleneoxide, such as ethylene oxide, propylene oxide, glycide, etc., to yielda perfectly satisfactory reactant for the herein described condensationprocedure. This can be illustrated in the following manner by a compoundsuch as zHhNHz 2-heptadeoyl,1-amiuoethylimidazoline which can be reactedwith a single mole of ethylene oxide, for example, to produce thehydroxy ethyl derivative of 2-heptadecyl,l-amino-ethylimidazoline, whichcan be illustrated by the following formula:

in the foregoing examples there is present a sizeable hydrophobe group,for instance, heptadecyl groups, pentadecyl groups, octyl groups, nonylgroups, etc. etc.

One can obtain all these comparable derivatives from low molal acids,such as acetic, propionic, butyric', valeric, etc. Similarly, one canemploy hydroxy acids such as glycolid acids, lactic acid, etc. Over andabove this, one may employ acids which introduce a very distincthydrophobe efiect.

BIT-CH3 H (18) NCH:

N-OH:

PART 4 The products obtained by the herein described processes representcogeneric mixtures which are the result of a condensation reaction orreactions. Since the resin molecule cannot bede'fined satisfactorily byformula, although it may be so illustrated in an idealizedsimplification, it is difiicult to actually depict the final product ofthe cogeneric mixture except in terms of the process itself. Thecondensation of the resin, the amidine and formaldehyde is described indetail in applications Serial Nos. 288,746 and 296,087, and reference ismade to those applications for a discussion of the factors involved.

Little more need be said as to the actual procedure employed for thepreparation of the herein described condensation products. The followingexample will serve by way of illustration:

Example 1b The phenoIealdehyde resin is the one that has been identifiedpreviously as Example 2a. It was obtained from a para tertiarybutylphenol and formaldehyde. The resin was prepared using an acidcatalyst which was completely neutralized at the end of the reaction.The molecular weight of the resin was 882.5. This corresponded to anaverage of about 3 /2 phenolic nuclei, as the value for n which excludesthe 2 external nuclei, i. e., the resin was largely a mixture having 3nuclei and 4 nuclei excluding the 2 external nuclei, or 5 and 6 overallnuclei. The resin so obtained in a neutral state had a light ambercolor.

to 6 hours.

were powdered and mixed with a somewhat lesser amount of xylene, i. e.,600 grams. The mixture was refluxed until solution was complete. It wasthen adjusted to approximately C. and 612 grams of 2-oleylimidazoline,previously shown in a structural formula as ring compound (3), wereadded. The mixture was stirred vigorously and formaldehyde added slowly.In this particular case the formaldehyde used was a 37% solution and 162grams were added in approximately 3 hours. The mixture was stirredvigorously and kept within a range of approximately 40 to 44 C., forabout 16 /2 hours. At the end of this time it was refluxed, using aphase-separating trap and a small amount of aqueous distillate withdrawnfrom time to time. The presence of unreacted formaldehyde was noted. Anyunreacted formaldehyde seemed to disappear in approximately three hoursafter refluxing started. As soon as the odor of formaldehyde was nolonger detectible the phaseseparating trap was set so as to eliminateall the water of solution and reaction. After the water was eliminatedpart of the xylene was removed until the temperature reachedapproximately 148 C. The mass was kept at this higher temperature for 3or 4 hours. During this time any additional water, which was probablywater of reaction which had formed, was eliminated by means of the trap.The residual xylene was permitted to stay in the cogeneric mixture. Asmall amount of the sample was heated on a Water bath to remove theexcess xylene. The residual material was dark red in color and had theconsistency of a thick sticky fluid or tacky resin. The overall reactiontime was approximately 30 hours. In other examples it varied from aslittle as 24 hours up to approximately 38 hours. The time can be reducedby cutting the low temperature period to approximately 3 Note that inTable II following there are a large number of added examplesillustrating the same procedure. In each case the initial mixture wasstirred and held at a fairly low temperature (30 to 40 C.) for a periodof several hours. Then refluxing was employed until the odor offormaldehyde disappeared. After the odor of formaldehyde disappeared thephase-separating trap was employed to separate out all the water, boththe solution and condensation. After all the water had V been separatedenough xylene Was taken out to have the final product reflux for severalhours somewhere in the range of 145 to 150 C., or thereabouts. Usuallythe mixture yielded a clear solution by the time the bulk of the Water,or all of the water, had been removed.

Note that as pointed out previously, this procedure is 882 grams of theresin ldentified as 2a, preceding, lllustrated by 24 examples in TableII.

TABLE II Strength 01 Iteac- Reac- Mar. Ex. Resin Amt., Amine used Amt.of formaldehyde Solvent used tion tlon distill N0. used grs. amine,soln. and amt. and amt. temp., time temp,

grams C. (his) C.

612 37%, 162 g Xyleno,600 g 2025 30 148 306 37 81 g. Xylene, 450 21-2324 145 306 A--. o Xylene, 600 g 20-22 28 150 281 r 30%, g.. Xylene, 400g 22-24 28 148 do Xylene, 450 g 21-23 30 148 26 146 26 147 26 146Xylene, 600 g.. 21- 25 38 150 Xylene, 450 gm. 2024 36 149 Xylene, 500 g2l-22 24 142 379 do Xylene, 650 EL... 20-21 26 145 395 38%, 81 g Xylene,425 22-28 28 140 395 37%, 81 g Xylene, 450 g 2330 27 d X 29 147 Xylene,440 20-21 30 148 Xylene, 480 g 21-26 32 146 Xylene, 600 a. 21-23 26 147Xylene, 500 g. 21-32 20 150 d0 21-30 32 1F Xylene, 550 g 21-23 37 150Xylene, 440 g. 2n-22 an 150 126 do Xylene, 600 g- 2025 30 149 126 30%,.50 'g. Xylene, 400 g. 20-24 32 ,152

is The amine numbers referred to are the ring compounds identifiedpreviously by number in Part 3.

PART

The conversion of the basic condensate of the kind previously describedinto the corresponding salt of gluconie acid is a simple operation sinceit is nothing more nor less than neutralization. The condensatesinvariably contain more than two basic nitrogen atoms. One canneutralize either one, or more, basic nitrogen atoms.

Gluconic acid is available as a 50% solution. Dehydration causesdecomposition. This is not true of the salts, at least not of the saltsof the herein described condensates. Such salts appear to be stable, orstable for all practical purposes, at temperatures slightly above theboiling point of water and perhaps at temperatures as high as 150 C. orthereabouts.

For reasons pointed out previously, it is most convenient to handle thecondensate as a solution, generally a solution in an inexpensivesolvent, such as benzene, xylene, an aromatic petroleum solvent, or thelike. A number of the condensates previously described have beenprepared in 50% solution as noted. Adding the calculated stoichiometricamount of 50% gluconic acid, calculated on the basis of the theoreticalbasic nitrogen atoms present, forms such salt which, in many instancesmay be slightly on the basic side and in other instances perhapsslightly on the acid side. The salt formation is merely a matter ofagitating at room temperature, or somewhat higher temperature ifdesired, particularly under a reflux condenser. After salt formation iscomplete, I have permitted the solution to stand for about 6 to 72hours. Some times, depending on the composition, there is someseparation of an aqueous phase. On a laboratory scale, this procedure isconducted in a separatory tunnel. If there is separation of an aqueousphase, the aqueous phase is discarded and the solution can be broughtback to a predetermined concentration by the addition of a hydrocarbonsolvent, such as xylene, or by the addition of an alcohol, such asmethyl, ethyl, or propyl alcohol; or, if need be, one can employ abridge solvent having hydrotropic properties in case of the'diethylether of ethyleneglycol, or similar solvents.

The gluconic salts can be obtained in non-aqueous solution by using aslightly modified procedure. The procedure depends on the fact that thephase-separating trap can be used but it is preferable to stay below 150C. so as to avoid any possible decomposition.

The xylene solution of the condensate, as previously described, issubjected to vacuum distillation so as to remove about one-half thexylene. Approximately twothirds of the xylene removed is replaced bybenzene. This mixed solvent combination is subjected to refluxing actionunder a condenser with a phase-separating trap. With the distillationpoint adjusted so as to be somewhere between 110 to 135 C. the mixtureis refluxed and the water separated. If it isnot within this range morebenzene is added or, if need be, a little more xylene is added to bringit within the range. By this method the phase-separating trap eliminatesthe water. The temperature at all times is left below 140 C. At the endof the separation a suitable amount of solvent is added, or eliminated,by distillation so as to yield a solution of predeterminedconcentration, for instance, 50%.

Using a somewhat similar procedure one can obtain the solvent-freematerial by merely subjecting the xylene solution of the condensate tovacuum distillation so as to remove all the xylene. The condensateitself is perfectly stable at 150 C. or thereabouts and, thus, there isno particular danger of degradation involved in this step. Thesolvent-free material is then dissolved in benzene instead of xylene andwater eliminated in the manner previously described. Thebenzene iseliminated by vacuum distillation in such a way that the temperaturenever gets above 135 C. or 140 C. Actually, with care the solutionpreviously described, to wit, the xylenebenzene solution, also can beremoved without decomposition.

An examination of the basic cyclic amidines employed indicates there maybe present at least three sub-genera. One sub-genera includes the typein which there is present a residual secondary amino group; anothersubgenera includes the type in which there is present a hydroxyl group,such as an ethanol group; and a third sub-genera contains both thesereactive groups. When such products are neutralized, particularly whenneutralization is complete, it becomes apparent that one has a materialwhich, in one way, is analogous to triethanolamine oleate; or, for thatmatter, triethanolamine gluconate. In another way the analogy is similarto diethanolamine oleate or diethanolamine gluconate. If diethanolamineoleate is heated it can be converted into oleyl diethanolamine, i. e.,involving an ester linkage. Similarly, if diethanolamine oleate isheated one can form the corresponding amide or perhaps under certainconditions, the corresponding ester. Obviously, esters can invariablyand inevitably form in regard to the completely neutralized product andeven in some cases in regard to the partially neutralized product. Thisis, of course, assuming that appropriate conditions of reaction areselected. In other instances where there is a residual secondary amineradical one may form amides or, for that matter mixtures of both amidesand esters. For this reason previous reference to decomposition must beconstrued to mean not only decomposition in the sense that degradationor inner ethers are formed, but also in the sense that an entirely newand valuable compound, or compounds, may be formed. Such reactions, ofcourse, form water as a by-product regardless of whether amidificationor esterification is involved.

Example 11), in turn, was made from resin 2a and amine 3 previouslydescribed in Part 3, preceding. 882 grams of the resin were dissolved inabout 600 grams of xylene and reacted with 612 grams of the cyclicamidine previously identified as amine 3, along with 162 grams of 3 7%formaldehyde. All this has been described previously. The weight of thecondensate on a solventfree basis was 1518 grams. This representedapproximately 53 grams of basic nitrogen subject to what is said in thenote following Table III which, in turn, immediately follows the presenttext.

To the above mixture, with constant stirring, there were added 1480grams of 50% gluconic acid. The mixture was stirred for one hour. Thissolution was poured into a separatory funnel or syphon arrangement andallowed to stand for about two days at 40 C. There was at the most aslight separation of insoluble material at the bottom of the separatoryfunnel. This was withdrawn and grams of isopropyl alcohol added andenough xylene to bring the final product to approximately a 50%solution.

A number of other examples are included in Table III, following.

essence TABLE III A Condensate in turn derived from Salt formation SaltSalt from Wt. of Final ex. eon- Amt. 37% conden- Theo. 50% wt. ad- No.den- Resin Amt. sol- Amine rmsate on basic glujusted to sate N o. resin,Solvent vent, Amine used 1 used, aldesolventnitroconic ap rox. No. gms.gms. gins. hyde, free gen, acid, 50 salt, gms. basis, gms. gms. 50%solv.,

gms. gms.

012 162 1, 518 53 l, 480 4, 516 306 798 27 720 2, 316 306 81 951 27 7202, 622 281 2 100 734 38 1,065 2, 533 281 I 100 773 38 1,065 2, 571 28181 826 38 ,065 2, 717 304 81 847 42 1, 175 2, 869 394 81 886 42 1, 1752, 947 394 81 1, 039 42 1, 175 3, 253 395 Z 100 880 42 1,175 2, 935 3952 100 916 42 1,175 3,007 395 1 100 1,069 42 1, 175 3, 313 612 162 1, 51827 720 3, 756 281 2 100 734 19 635 2, 003 395 7 100 880 21 585 2, 345

i For identification of amine numbers see ring compounds in Part 3. 1formaldehyde. 3 See text following.

Ordinarily the two nitrogens in the ring compound give a basic effectless than the equivalent of two separate nitrogen atoms but in the orderof 1.7 nitrogen atom. In some examples, particularly 1c, 20, 3c, and10c, 11c, 12c, together with 130 and 150, the amount of ring compoundwas somewhat in excess of the molecular portion of 2, 1 and 2 incondensate formation. These two factors explain variation in amount ofgluconic acid used for salt formation.

PART 6 Conventional demulsifying agents employed in the treatment of oilfield emulsions are used as such, or after dilution with any suitablesolvent, such as Water, petroleum hydrocarbons, such as benzene,toluene, x lene, tar acid oil, crcsol, anthracene oil, etc. Alcohols,particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol,denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octylalcohol, etc., may be employed as diluents. Miscellaneous solvents suchas pine oil, carbon tetrachloride, sulfur dioxide extract obtained inthe refining of petroleum, etc., may be employed as diluents. Similarly,the material or materials employed as the demulsifying agent of myprocess may be admixed with one or more of the solvents customarily usedin connection with conventional demulsifying agents. More over, saidmaterial or materials may be used alone or in admixture with othersuitable Well-known classes of de mulsifying agents.

It is well known that conventional demulsifying agents may be used in awater-soluble form, or in an oil-soluble form, or in a form exhibitingboth oiland water-solubility. Sometimes they may be used in a form whichexhibits relatively limited oil-solubility. However, since such reagentsare frequently used in a ratio of 1 to 10,000 or 1 to 20,000, or 1 to30,000, or even 1 to 40,000, or 1 to 50,000 as in desalting practice,such an apparent insolubility in oil and water is not significantbecause said reagents undoubtedly have solubility Within suchconcentrations. This same fact is true in regard to the material ormaterials of my invention when employed as demulsifying agents.

The materials of my invention, when em loyed as treating of demulsifyingagents, are used in the conventional way, Well known to the art,described, for example, in Patent 2,626,929, dated January 27, 1953,Part 3, and reference is made thereto for a description of conventionalprocedures of demulsifying, including batch, continuous, anddown-the-hole demulsification, the process essentially involvingintroducing a small amount of demulsifier into a large amount ofemulsion with adequate admixture with or without the application ofheat, and allowing the mixture to stratify.

As noted above, the products herein described may be used not only indiluted form, but also may be used admixed with some other chemicaldemulsifier. A mixture which illustrates such combination is thefollowing:

Gluconic acid salt, for example, the product of Example lc, 20%;

A cyclohexylamie salt of a polypropylated napthalene monosulfonic acid,24%;

An ammonium salt of a polypropylated napthalene monosulfonic acid, 24%;

A sodium salt of oil-soluble mahogany petroleum sulfonic acid, 12%;

A high-boiling aromatic petroleum solvent, 15%;

Isopropyl alcohol, 5%.

The above proportions are all weight percents.

PART 7 The gluconic acid salts herein described can be used asemulsifying agents for oils, fats, and waxes; as ingredients ininsecticidecompositions; or as detergents and Wetting agents in thelaundering, scouring, dyeing, tanning and mordanting industries. Also,they can be used for preparing boring or metal-cutting oils and cattledips, as metal pickling inhibitors, and for pharmaceutical purposes.Also, the gluconic acid salts are useful in dry cleaners soaps.

Also, they may be used as additives in connection with other emulsifyingagents; they may be employed to contribute hydrotropic effects; they maybe'used as antistrippers in connection with asphalts; they may be usedto prevent corrosion, particularly the corrosion of ferrous metals forvarious purposes and particularly in connection with the production ofoil and gas, and also in refineries where crude oil is converted intovarious commercial products. The products may be used industrially toinhibit or stop microorganic growth or other objectionable lower formsof life, such as the growth of. algae, or the like; they may be used toinhibit the growth of bacteria, molds, etc.; they are valuable additivesto lubricating oils, both those derived from petroleum and syntheticlubricating oils, and also to hydraulic brake fluids of the aqueous ornon-aqueous type; some have definite anti-corrosive action. They may beused in connection with other processes where they are injected into anoil or gas well for purpose of removing a, mud sheath, increasing theultimate flow of fluid from able, as has been pointed out, to theforrnation of. oleyl triethanolamine from triethanolamine oleate, or theamine from diethanolamineoleate. Such cyclic amidines which have inaddiiton the ester group, or amide group, or both either alone or insaltcombination are valuable for all the various purposes describedimmediately preceding and particularly for the resolution of petroleumcmulsions of of the water-in oil type, in the resolution of petroleumemulsions of the 'oil-in-water type, for the prevention of corrosion offerrous metals, and as an asphalt additive for anti-stripping purposes.In such instances where the ester is formedtexclusively it can bereacted again with an acid in the same manner that oleyl triethanolaminecan be converted into a salt. Indeed, the

salt obtained byjombination with an oil-soluble petroleum acid, i. e.,mahogany acid, is particularly valuable for the prevention o fcorrosion. H

Previous referencehas been made to oxyalkylation, and particularlyoxyethylation and oxypropylation. The condensate prior to conversioninto a salt is oxyalkylatioususceptible Gluconic acid includes as partof its structure hydroxyl groups which are oxyalkylation-susceptible.Thus, it follows that thesalt of the condensate contains one or moregroups indeed a plurality of groups in which a labile hydrogen atomappears, and thus are, in turn, oxyalkylation-susceptible. However, itis usually difiicult, indeed extremely difficult, at times tooxyalkylate in presence of-a radical which is in essence a salt as inthe present case. For this reason it is more practical and moreeconomical to convert the condensate into an oxyalkylated derivative andthenconvert the oxyalkylated derivative into a salt of gluconic acid.Such type of compound, or cogeneric mixture, is not within the scope ofthe present invention.

Having thus described my invention, what I claim as new and desire tosecure by; Letters Patent is:

1. A two-step manufacturing process including the method of condensing(a) an oxyalkylation-susceptible, fusible, non-oxygenated organicsolventsoluble, waterinsoluble, low-stage phenol-aldehyde resin havingan average molecular weight corresponding, to at least 3 and not over 6phenolic nuclei per resin molecule; said resin eing difunctional only inregard to methylol-forming reactivity; said resin being derived'byreaction between a difunctional monohydric phenoland 'an aldehyde havingnot over 8 carbon atoms and reactive toward said phenol; said resinbeing formed in the substantial absence of trifunctional phenols; saidphenol being of the formula in which R is a saturated aliphatichydrocarbon radical having at least 4 and not more than24 carbon atomsand substituted in the 2,4, 6position; (b) cyclic amidines selectedfrom1the c1ass consisting of substituted imidazolines and substitutedtetrahydropyrimidines in whichthere is present at least one basicsecondary amino radical and characterized by freedom from any primaryamino radical; and (0) formaldehyde; said condensation reaction beingconducted at a temperature sulficiently high to eliminate water andbelow the pyrolytic point of the reactants and resultants of reaction,with the proviso that the condensation reaction be conducted so as toproduce a significant portion of the resultant in which each of thethree reactants have contributed part of the ultimate molecule by virtueof a formaldehyde-derived methylene bridge connecting the amino nitrogenatom with a resin molecule; and with the further proviso that theresinous condensation product resulting from the process be heatstable;and followed by neutralization with gluconic acid.

2. A two-step manufacturing process including the method of condensing(a) an oxyalkylation-susceptible, fusible, non-oxygenated organicsolvent-soluble, waterinsoluble, low-stage phenol-aldehyde resin havingan average molecular Weight corresponding to at least 3 and not over 6phenolic nuclei per resin molecule; said resin being difunctional onlyin regard to methylol-forming reactivity;

said resin being derived by reaction between, a difunctional monohydricphenol and an aldehyde having not over 8 carbon atoms and reactivetoward said phenol; said resin being formed in the substantial absenceof trifunctional phenols; said phenol being of the formula in which R isa saturated aliphatic hydrocarbon radical having at least 4 and not morethan 24 carbon atoms and substituted in the 2,4,6position; (b) cyclicarnidines selected from the class consisting of substitutedirnidazolines and substituted tetrahydropyrimidines in which there ispresent at least one basic secondary amino radical and characterized byfreedom from any primary amino radical; and (c) formaldehyde; saidcondensation reaction being conducted at a temperature sufiiciently high.to eliminate water and below the pyrolytic pointiof the reactants andresultants of reaction; with the proviso that the condensation reactionbe conducted so as to produce a significant portion of the resultant inwhich each of the three reactants have contributed part of the ultimatemolecule by virtue of a formaldehyde-derived methylene bridge connectingthe amino nitrogen atom with a resin molecule; with the further provisothat the molar-ratio of reactants be approximately 1, 2 and 2respectively; and with the final proviso that the resinous condensationproduct resulting from the process be heat-stable; and followed byneutralization with gluconic: acid.

3. A two-step manufacturing process including the method of condensing(a) an oxyalkylation-susceptible, fusible, non-oxygenated organicsolvent-soluble, waterinsoluble, low-stage phenol-aldehyde resin havingan average molecular weight corresponding to at least 3 and not over 6phenolic nuclei per resin molecule; said resin being difunctional onlyin regard to methylol-forming reactivity; said resin being derived byreaction between a difunctional monohydric phenol and an aldehyde havingnot over 8 carbon atoms and reactive toward said phenol; said resinbeing formed in the substantial absence of trifunctional phenols; saidphenol being of the formula eliminate water and below the pyrolyticpoint of the reactants and resultants of reaction, with the proviso thatthe condensation reaction be conducted so as to produce a significantportion of the resultant in which each of the t-hreereactants havecontributed part of the ultimate molecule by virtue of aformaldehyde-derived methylene bridge Connecting the amino nitrogen atomwith a resin molecule; with the added proviso that the molar ratio ofreactants be approximately 1, 2 and 2, respectively; with the furtherproviso that said procedure volve the use of a solvent; and with thefinal proviso that the resinous condensation product resulting from theprocess be hea stable; and followed by neutralization with gluconicacid.

4. A two-step manufacturing process including the method of condensing(a) an oXyethylation-sasceptible, fusible, non-oxygenated organicsolvent-soluble, water-insoluble, low-stage phenol-formaldehyde resinhaving an average molecular weight corresponding to at least 3 and notover 6 phenolic nuclei per resin molecule; said resin being difunctionalonly in regard to methylol-forming reactivity; said resin being derivedby reaction between a difunctional monohydric phenol and formaldehyde;said resin being formed in the substantial absence of trifunctionalphenols; said phenol being of the formula in which R is a saturatedaliphatic hydrocarbon radical having at least 4 and not more than 14carbon atoms and substituted in the 2,4,6 position; (b) cyclic amidinesselected from the class consisting of substituted imidazolines andsubstituted tetrahydropyrimidines in which there is present at least onebasic secondary amino radical and characterized by freedom from anyprimary amino radical; and formaldehyde; said condensation reaction being conducted at a temperature sufiiciently high to eliminate water andbelow the pyrolytic point of the reactants andresultants of reaction,with the proviso that the condensation reaction be conducted so as toproduce a significant portion of the resultant in which each of thethree reactants have contributed part of the ultimate molecule by virtueof a formaldehyde-derived methylene bridge connecting the amino nitrogenatom with a resin molecule; with the added proviso that the molar ratioof reactants be approximately 1, 2 and 2, respectively; with the furtherproviso that said procedure involve the use of a solvent; and with thefinal proviso that the resinous condensation product resulting from theprocess be heat-stable; and followed by neutralization with gluconicacid.

'5. A two-step manufacturing process including the method of condensing(a) an oxyethylanon-susceptible, fusible, non-oxygenated organicsolvent-soluble, water-insoluble, low-stage phenol-formaldehyde resinhaving an average molecular weight corresponding to at least 3 and notover .5 phenolic nuclei per resin molecule; said resin beingdifunctional only in regard to methylol-forming reactivity; said resinbeing derived by reaction between a difunctional monohydric phenol andformaldehyde; said resin being formed in the substantial absence oftrifunctional phenols; said phenol being of the formula in which R is asaturated aliphatic hydrocarbon radical having at least 4 and not morethan 14 carbon atoms and substituted in the 2,4,6 position; (b) cyclicamidines selected from the class consisting of substituted imidazolinesand substituted tetrahydropyrimidines in'which-the'r'e is present atleast one basic secondary amino radica'l'and characterized by freedomfrom any'primary amino radical; and (0) formaldehyde; said condensationreaction being conducted at a temperature sufficiently high to eliminatewater and below the pyrolytic point of the reactants and resultants ofreaction, with the proviso that the condensation reaction be conductedso as to produce a significant portion of the resultant in which each ofthe three reactants have contributed part of the ultimate molecule byvirtue of a formaldehyde-derived methylene bridge connecting the aminonitrogen atom with a resin molecule; with the added proviso that themolar ratio of reactants be approximately 1, 2 and 2, respectively; withthe further proviso that said procedure involve the use of a solvent;and with the final proviso that thevresinous condensation productresulting from the process be heatstable; and followed by neutralizationwith gluconic acid.

6. A two-step manufacturing process including the method of condensing(a) an oxyethylation-susceptible, fusible, non-oxygenated organicsolvent-soluble, water-insoluble, low-stage phenol-formaldehyde resinhaving an average molecular weight corresponding to. at least 3 and notover 5 phenolic nuclei per resin molecule; said resin being difunctionalonly in regard to methylol-forming reactivity; said resin being derivedby reaction between a difunctional monohydric phenol and formaldehyde;said resin being formed in the substantial absenceof trifunctionalphenols; said phenol being of the formula in which R is a saturatedaliphatic hydrocarbon radical having at least 4 and not more than 14carbon atoms and substituted in the 2,4,6 position; (b) cyclic amidinesselected from the class consisting of substituted 'imidaz0- lines andsubstituted tetrahydropyrirnidines in which there is present at leastone basic secondary amino radical and characterized by freedom from anyprimary amino radical; and (0) formaldehyde; said condensation reactionbeing conducted at a temperature above the boiling point of water andbelow C., with the proviso that the condensation reaction be conductedso as'to produce a significant portion of the resultant in which each ofthe three reactants have contributed part of the ultimate molecule byvirtue of a formaldehyde-derived methylene bridge connecting the aminonitrogen atom with a resin molecule; with the added proviso that themolar ratio of reactants be approximately 1, 2 and 2, respectively; withthe further proviso that said procedure involve the use of a solvent;and with the final proviso that the resinous condensation productresulting from the process be heatstable; and followed by neutralizationwith gluconic acid.

7. The method of claim 6 where R is substituted in the para position.

8. The product resulting from the process defined in claim 1.

References Cited in the file of this patent UNITED STATES PATENTS1,996,069 Honel Apr. 2, 1935 2,031,557 Bruson Feb. 18, 1936 2,499,365 DeGroote Mar. 4, 1950

1. A TWO-STEP MANUFACTURING PROCESS INCLUDING THE METHOD OF CONDENSING(A) OXYALKYLATION-SUSCEPTIBLE FUSIBLE, NON-OXYGENATED ORGANICSOLVENT-SOLUBLE, WATERINSOLUBLE, LOW-STAGE PHENOL-ALDEHYDE RESIN HAVINGAN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLYIN REGARD TO METHYLO-FORMING REACTIVITY; SAID RESIN BEING DERIVED BYREACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVINGNOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESINBEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAIDPHENOL BEING OF THE FORMULA